CN112625413B - Modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material - Google Patents
Modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material Download PDFInfo
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- CN112625413B CN112625413B CN202011494480.3A CN202011494480A CN112625413B CN 112625413 B CN112625413 B CN 112625413B CN 202011494480 A CN202011494480 A CN 202011494480A CN 112625413 B CN112625413 B CN 112625413B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
- A61F5/01—Orthopaedic devices, e.g. splints, casts or braces
- A61F5/04—Devices for stretching or reducing fractured limbs; Devices for distractions; Splints
- A61F5/05—Devices for stretching or reducing fractured limbs; Devices for distractions; Splints for immobilising
- A61F5/058—Splints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a modified poly (4-hydroxybutyrate) low-temperature thermoplastic plate and a preparation method thereof. The invention takes poly (4-hydroxybutyrate) as a first component, and adds a reinforcing agent as a second component and a third component compatilizer. The materials are melted, blended, extruded and irradiated to prepare the medical low-temperature thermoplastic sheet, and the low-temperature thermoplastic sheet can be used for fixing hard tissues or soft tissues of human bodies. The low-temperature thermoplastic plate provided by the invention has the characteristics of excellent mechanical property, good biocompatibility, low-temperature thermoplastic property, low price and the like.
Description
Technical Field
The invention relates to the field of medical instruments, in particular to a modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material and a preparation method thereof.
Background
The external fixation treatment technology can effectively avoid the movement of the fracture part of the injured bone and prevent the occurrence of secondary injury. The first generation of external fracture fixation materials are mainly based on plaster of paris, and are widely applied clinically due to the characteristics of low price, easy molding and the like. However, the gypsum external fixation material has the disadvantages of low strength, heavy weight, poor radiation permeability and the like, and brings great inconvenience to patients in the clinical application process.
The second generation of bone external fixation materials are based on polymer composite materials. The composite material of the glass fiber cloth impregnated polyurethane is a preferable substitute for the gypsum splint because of the advantages of high curing speed, high strength, strong air permeability, good ray transmission performance, portability, durability, water resistance and the like. However, such splints need to be manufactured by casting and still do not meet the need for rapid rescue in emergency. In addition, the clamping plates cannot simultaneously have the requirements of high mechanical strength, repeatability, easy molding, low price and the like. In particular, if the fracture part of the splint is improperly fixed, the structure of the splint is difficult to change after curing, and the splint needs to be crushed and then a new splint is cast again.
The low-temperature thermoplastic plate is an emerging medical splint with strong plasticity, memory function, good air permeability, light weight, high strength and adhesiveness; the X-ray has the advantages of excellent permeability, easy detachment, degradability and the like, and becomes the first choice of the vast doctor and patient. Currently, polycaprolactone materials have been widely used to prepare medical low temperature thermoplastic sheets (CN 1408766, CN109608842 a).
Poly (4-hydroxybutyrate) (P4 HB) has a melting point of about 60℃and a glass transition temperature of about-51℃and is transparent and softenable in hot water at 60-70℃and can be rapidly cured at ordinary temperature or by means of an air cooler. In addition, P4HB has excellent biocompatibility, and surgical sutures and hernia patches prepared therewith have been approved by the U.S. food and drug administration (u.s.food and Drug Administration, u.s.fda).
Disclosure of Invention
The invention aims to prepare a novel medical poly (4-hydroxybutyrate) low-temperature thermoplastic plate applicable to fixing hard tissues or soft tissues of human bodies, and provides a preparation method based on the material.
The invention is realized by the following technical scheme:
the material comprises the following components, wherein the first component is thermoplastic poly (4-hydroxybutyrate), and the second component is a reinforcing material and a third component compatilizer. The thermoplastic polymer is the continuous phase and the reinforcing material is the dispersed phase. The material is melt-blended for 10-20 minutes in a melt state at 90-180 ℃, and the low-temperature thermoplastic sheet material is obtained after passing through a low-temperature thermoplastic sheet machine production line and being subjected to irradiation treatment.
The invention adopts the mixture ratio (mass fraction):
80-95wt% of poly (4-hydroxybutyrate)
5-20wt% of reinforcing agent
0.5-5wt% of compatilizer
The weight average molecular weight of the poly (4-hydroxybutyrate) is 1 ten thousand to 30 ten thousand.
The reinforcing agent is one or more of polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate, polybutylene succinate, nano lignin, nano cellulose, nano starch, talcum powder and calcium carbonate.
The compatilizer is one or more of maleic anhydride, dicumyl peroxide, di-tert-butyl diisopropyl peroxide, lysine triisocyanate, toluene diisocyanate, glycidyl methacrylate and a silane coupling agent.
The melt blending is performed in one of an internal mixer, a twin screw extruder or a single screw extruder.
The irradiation treatment adopts high-energy electron beams or gamma rays, and the irradiation treatment dosage is 40-150kGy.
The thickness of the low-temperature thermoplastic plate is 1.0mm-20mm
Compared with the prior art, the invention has the beneficial effects that:
the novel medical poly (4-hydroxybutyrate) low-temperature thermoplastic plate prepared by the invention has excellent low-temperature thermoplastic property, mechanical strength and air-permeability waterproof property; no cytotoxicity, no skin irritation and sensitization. The raw materials are derived from biomass, can be completely degraded, and the price is greatly reduced compared with the similar PCL products.
Detailed Description
The present invention will be described in further detail by the following detailed description, but it should not be construed that the scope of the invention is limited to the following examples. Various substitutions and alterations are also within the scope of this disclosure, as will be apparent to those of ordinary skill in the art and by routine experimentation, without departing from the spirit and scope of the invention as defined by the foregoing description.
Example 1
80wt% of poly (4-hydroxybutyrate)
Nano lignin 20wt%
The materials are evenly mixed and melt-blended for 15 minutes in an internal mixer at 110 ℃ to obtain a blended material. And then producing a plate with the thickness of 2mm by low-temperature thermoplastic plate production equipment, and finally adopting gamma ray irradiation treatment, wherein the irradiation dose is 100kGy. The Young modulus of the obtained material is 415+/-3 Mpa, the deformation recovery rate is 93.1+/-0.3%, and the shrinkage force is 32.1+/-2.0N.
Example 2
Poly (4-hydroxybutyrate) 85wt%
5wt% of poly-3-hydroxybutyrate
10wt% of nanocellulose
The materials are evenly mixed and melt-blended for 10 minutes in an internal mixer at 130 ℃ to obtain a blended material. And then producing a plate with the thickness of 8mm by low-temperature thermoplastic plate production equipment, and finally adopting gamma ray irradiation treatment, wherein the irradiation dose is 80kGy. The Young's modulus of the obtained material is 395+ -5 Mpa, the deformation recovery rate is 96.5+ -0.6%, and the shrinkage force is 25.1+ -1.3N.
Example 3
80wt% of poly (4-hydroxybutyrate)
5wt% of poly (3-hydroxybutyrate-co-4-hydroxybutyrate)
Poly (butylene succinate) 10wt%
Toluene diisocyanate 5wt%
The materials are evenly mixed and melt-blended for 20 minutes in an internal mixer at 160 ℃ to obtain a blended material. And then producing a plate with the thickness of 10mm by low-temperature thermoplastic plate production equipment, and finally adopting high-energy electron beam irradiation treatment, wherein the irradiation dose is 100kGy. The Young modulus of the obtained material is 312+/-1 Mpa, the deformation recovery rate is 90.5+/-1.6%, and the shrinkage force is 33.3+/-2.1N.
Example 4
80wt% of poly (4-hydroxybutyrate)
5wt% of poly (3-hydroxybutyrate-co-4-hydroxybutyrate)
5wt% of calcium carbonate
Lysine triisocyanate 10wt%
The materials are evenly mixed and melt-blended for 15 minutes in an internal mixer at 150 ℃ to obtain a blended material. And then producing a plate with the thickness of 10mm by low-temperature thermoplastic plate production equipment, and finally adopting high-energy electron beam irradiation treatment, wherein the irradiation dose is 40kGy. The Young modulus of the obtained material is 368+/-5 Mpa, the deformation recovery rate is 98.9+/-0.6%, and the shrinkage force is 49.3+/-5.1N.
Claims (6)
1. The modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material is characterized by comprising the following components, wherein the first component is thermoplastic poly (4-hydroxybutyrate), and the second component is a reinforcing material and a third component compatilizer;
the mass fraction of the thermoplastic poly (4-hydroxybutyrate) is 80-85wt%;
the reinforcing material comprises 10-20wt% of one or more of polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate, polybutylene succinate, nano lignin, nano cellulose, nano starch, talcum powder and calcium carbonate;
the mass fraction of the compatilizer is 0.5-5wt%, and the compatilizer is one or more selected from maleic anhydride, dicumyl peroxide, di-tert-butyl diisopropyl benzene peroxide, lysine triisocyanate, toluene diisocyanate, glycidyl methacrylate and silane coupling agent;
the modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material is prepared by uniformly mixing thermoplastic poly (4-hydroxybutyrate), reinforcing materials and compatilizer, melting and blending in a melting and blending instrument, and then adopting gamma ray irradiation treatment.
2. The modified poly (4-hydroxybutyrate) material of claim 1, wherein the poly (4-hydroxybutyrate) has a weight average molecular weight of 10000-300000.
3. The modified poly (4-hydroxybutyrate) low temperature thermoplastic medical splinting material of claim 1 wherein the melt blending apparatus is one of an internal mixer, a twin screw extruder or a single screw extruder.
4. The modified poly (4-hydroxybutyrate) low temperature thermoplastic medical splint material according to claim 1, wherein the melt blending temperature is 90-180 ℃ and the melt blending time is 10-20 minutes.
5. The modified poly (4-hydroxybutyrate) low temperature thermoplastic medical splint material according to claim 1, wherein the irradiation treatment is with high energy electron beam or gamma ray, and the irradiation treatment dose is 40-150kGy.
6. The modified poly (4-hydroxybutyrate) low temperature thermoplastic medical splint material according to claim 1, wherein the low temperature thermoplastic plate has a thickness of 1.0mm-20mm.
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| CN202011494480.3A CN112625413B (en) | 2020-12-17 | 2020-12-17 | Modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material |
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| CN102070891B (en) * | 2010-12-24 | 2012-08-22 | 中科院广州化学有限公司 | Polyester composite filled with lignin and preparation method thereof |
| EP3122817B1 (en) * | 2014-03-27 | 2020-07-29 | CJ CheilJedang Corporation | Highly filled polymer systems |
| CN104130562A (en) * | 2014-07-28 | 2014-11-05 | 江苏嘉铂新材料有限公司 | Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof |
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